US3860565A - Encapsulated isocyanurate catalyst - Google Patents
Encapsulated isocyanurate catalyst Download PDFInfo
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- US3860565A US3860565A US402409A US40240973A US3860565A US 3860565 A US3860565 A US 3860565A US 402409 A US402409 A US 402409A US 40240973 A US40240973 A US 40240973A US 3860565 A US3860565 A US 3860565A
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- Prior art keywords
- catalyst
- isocyanate
- polyisocyanate
- isocyanurate
- activating force
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/902—Cellular polymer containing an isocyanurate structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S528/902—Particulate material prepared from an isocyanate
Definitions
- ABSTRACT A one-part, room temperature-latent isocyanatecatalyst system trimerizable to polyisocyanurate is formed comprising an aromatic isocyanate having dispersed throughout liquid microcapsules of a catalyst for isocyanurate formation.
- microcapsules have a permeable shell wall essentially of partially polymerized aromatic isocyanates which encapsulates the liquid catalyst at room temperature but on activation of the isocyanate-catalyst system by a suitable force the liquid catalyst permeates the shell wall, mixes with the polyisocyanate, and cures the isocyanate to a fully cured thermoset isocyanurate material.
- this invention relates to one-part isocyanate-catalyst systems curable to isocyanurate resins.
- this invention relates to encapsulated catlaysts.
- this invention relates to a process for encapsulating catalysts.
- Known catalysts for trimerizing isocyanates can be divided into two general classes. First, those which cause trimerization of isocyanate exothermically at room temperature and second, those which trimerize isocyanates only at elevated temperatures and prolonged reaction times.
- the first group lacks latency and therefore may be used only in two-part compositions.
- the second group of catalysts generally has a short shelf life, e.g. several weeks and requires long cure times, on the order of several hours at elevated temperatures.
- Curable resin compositions containing encapsulated catalysts are known. Examples of such compositions are disclosed in U.S. Pat. No. 3,018,258 which teaches polyepoxide compositions containing capsules, having a hardened inactive colloid shell wall, e.g. gelatin, about a curing agent. Therefore, such compositions are substantially unreactive under normal temperatures, having a shelf life of several months, but cure on prolonged heating, e.g. 24 hours.
- U.S. Pat. No. 3,455,848 teaches stable compositions which contain an intimate mixture of polyurethane components, at least one of the components being in capsules having a shell wall of gelatin. On heating the composition, the encapsulated component reacts with the unencapsulated component or components to form a polyurethane.
- U.S. Pat. No. 3,467,544 teaches resin compositions comprising an encapsulated polysulfide, the gelatincapsule wall contains a metal oxide catalyst suitable for curing the polysulfide, Upon rupture of the capsules, polysulfide is released contacting the catalyst, and curing takes place.
- U.S. Pat. No. 3,505,254 teaches polysulfide compositions containing encapsulated metal oxide, which cures upon breaking the capsule shell walls which can be lignin sulfonates, phenol, formaldehyde penterythritrol esters, etc.
- Patents describing such pro Rous and their shell wall material include U.S. Pat. Nos. 1,800,458, hydrophobic colloids; 3,069,370; 3,116,206, polymeric zinc; 3,137,631, denatured proteins; 3,418,250, hydrophobic thermoplatic resins; and others.
- Another such process is complex coacervation microencapsulation. By this process a polymer having an electric charge of one polarity is caused to separate from solution by the addition of a polymer having the opposite polarity.
- Patents describing such processes include U.S. Pat. Nos. 2,800,457, complex colloid; 3,317,434, gelatin; 3,324,065; and others.
- a shell wall is formed about suspended particulate material by an interfacial polycondensation reaction.
- the material to be encapsulated is mixed with a solution of one component of a polycondensation reaction and the mixture dispersed in a nonsolvent for the mixture.
- a second component of the polycondensation reaction is added to the resulting dispersion.
- the subsequent reaction forms a shell wall of polycondensate about each dispersed droplet at its interface.
- microencapsulation is by an interfacial addition polymerization.
- a particulate material is suspended in a solution of a polymerizable, ethylenically unsaturated compound in a solvent.
- This solvent is not a solvent for the polymer formed from unsaturated compound.
- the unsaturated compound is polymerized such as by the use of free radical initiators.
- the resulting polymer forms a shell wall about the suspended particulate material.
- Patents describing such processes include U.S. Pat. Nos. 3,516,725; 3,427,250; 3,565,818; 3,575,882; 3,577,515; 3,594,328; and others.
- a room-temperature latent, onepart, triggerable isocyanate-catalyst system which comprises: polyisocyanate material, e.g., polyisocyanates, diisocyanate, and isocyanate-terminated prepolymers, having dispersed therein an encapsulated liquid isocyanate trimerization catalyst having a viscosity greater than about 5000 centipoise at 25C.
- the trimerization catalyst is encapsulated in a permeable capsule having a shell wall of partially polymerized isocyanate, said capsule being impermeable to the liquid catalyst at room temperature but permeable to said catalyst at about C.
- the permeable capsules are formed by an in situ interfacial polymerization reaction with polyisocyanate material, the resulting capsules being dispersed throughout the isocyanate-terminated material and there is no need for the intermediate step of isolating the capsules as is common in prior art processes.
- the isocyanate-catalyst resin system can be triggered, that is rendered active for further reaction, by the application of an activating force, e.g. heat, ultrasonic waves, mechanical shear, polar solvents which cause permeation of the liquid catalyst through the shell wall. Release of the catalyst from the capsule then promotes a complete, rapid room temperature cure of the entire mass of isocyanate material to isocyanurate resin.
- the permeable, partially polymerized material is able to so effectively isolate the catalyst from the remainder of the polyisocyanate that the system can be stored at room temperature (or even somewhat higher temperatures) for months or even years yet curing is completed in minutes upon activation.
- the isocyanate trimerization catalysts used in the latent, one-part, triggerable isocyanate-catalyst system of this invention comprise a viscous liquid catalyst solution, preferably a solution of an alkali metal salt of an organic acid encapsulated in microcapsules.
- the microcapsules are prepared in situ, in a polyisocyanate material, by the addition of the liquid catalyst to the polyisocyanate under conditions of shear.
- the polyisocyanate is maintained at a temperature above the melting point of the polyisocyanate material but below about 50C., and preferably below about 40C., to avoid premature trimerization of the polyisocyanate.
- the microcapsules prepared under these conditions have a shell wall which is essentially partially polymerized aromatic isocyanate.
- the wall is of such a nature that it contains the viscous solution of alkali metal salt at temperatures below about 50C. However, at temperatures above about 75C. the viscosity of the alkali metal salt solution is reduced to less than about 5,000 centipoise, allowing the alkali metal salt solution to penetrate the shell wall, mix with the isocyanate material, and initiate polymerization of the aromatic polyisocyanate material.
- the material of the capsule walls Upon isolation of the microcapsules from the isocyanate system the material of the capsule walls apparently reacts further to an essentially completely trimerized isocyanurate. The resulting capsule walls are less permeable to alkali metal salt solutions, even at temperatures above about 50C., and activation of a system using these capsules would require temperatures above about 150C. or higher.
- Suitable alkali metal salts for use in a liquid catalyst solution are those alkali metal salts of organic acids having a pK, between about 2.5 and 10, preferably between about 3 and 6.
- the acids with a pK of about 3 6 provide catalysts that are easily synthesized, give good shelf stability when dispersed in isocyanate materials, yet cure rapidly when activated.
- the alkali metal salts used in this invention are alkali metal salts of monoor polycarboxylic acids and phenols having from 2 to about 8 carbon atoms and are preferably monoand polycarboxylic acids having 2 to carbon atoms.
- the alkali metal salts of organic acids having more than about 8 carbon atoms generally have a higher solubility in isocyanates,
- alkali metal salts for use in this invention include sodium lactate, potassium lactate, rubidium lactate, potassium glycolate, potassium hydroxyisobutyrate, potassium Z-hydroxypropionate, potas sium acetate, potassium butyrate, sodium butyrate, lithium octoate, potassium cyanoacetate, dipotassium oxalate, disodium succinate, dilithium adipate, dipotassium adipate, potassium mandelate, disodium phthalate, sodium phenoxide, potassium p-chlorophenoxide, sodium m-cresoxide, and the like.
- the solubility of the alkali metal salt catalysts in polyols is such that the catalyst solution will generally contain more than 15 percent by weight salts, preferably about 50 percent by weight or more.
- the resulting solutions will generally have a viscosity of at least 5,000 centipoise or greater at temperatures up to about 50C., preferably a viscosity greater than about 100,000 centipoise at temperatures up to about 40C.
- the lower viscosity materials yield microcapsules that give partially and nonhomogeneously cured resins even after prolonged heating at elevated temperatures. Furthermore the shelf stability of these systems is signifi cantly reduced as compared to the higher viscosity liquid catalyst solutions.
- Solvents which can be used to dissolve the alkali metal salts, to form a viscous catalysts solution are generally polar organic compounds and preferably have a boiling point sufficiently higher than water so that the solvent can be made essentially anhydrous, i.e. have a water content of one percent or less, by azeotropic distillation.
- solvents examples include lower polyhydric alcohols having 2 to about 8 carbon atoms, such as ethylene glycol, propylene glycol, glycerin, 1,4-butanediol, l,2,4-butanetriol, 2,2 oxydiethanol, 3,3 -oxydipropanol, 1,1,1- trimethylolpropane, l,2,3-trimethylolpropane, and the like and mixtures of such polyhydric alcohols; formamide, N-methyl-formamide, ethylene carbonate, 4- butyrolactone, pyrrolidone, N-methyl pyrrolidone, and the like and mixtures of such solvents.
- the preferred solvents are the lower polyhydric alcohols, and glycerol is the most preferred.
- a preferred catalyst solution is an alkali metal salt 0 lactic acid in glycerol.
- This catalyst solution when dis persed in polyisocyanate, especially Mondur MRS, gives consistently good catalyst-containing capsules which are efficient in releasing the catalyst and giving cured resins with good physical properties, including thermal stability, hydrolytic stability and useful dielectric properties.
- the catalyst solution can be directly synthesized by mixing the alkali metal salt and solvent or alternatively, the viscous catalyst solution may be prepared by reacting alkali metal salt precursors in a solution of the selected solvent to form the desired catalyst and subse 1 quently azeotroping off any resulting water using an azeotroping fluid such as toluene to form a substantially anhydrous catalyst solution. After azeotroping, any remaining organic solvents can be removed, e.g. by
- a potassium lactate-glycerol catalyst solution can be prepared by reacting an aqueous solution of lactic acid with potassium hydroxide in a minimum of water and glyccrine. Toluene is added to the mixture, and the reaction vessel is fitted with a water separator. The solution is then azeotroped until no more water can be driven off the reaction mixture. At this point, the solution generally contains 1% or less of water. After the water is removed, the toluene is removed by reduced pressure distillation.
- the encapsulation of the isocyanate trimerization catalyst solution using a polyisocyanate can be performed in batches or continuously.
- a unit capable of providing a fine dispersion of the catalyst solution in the aromatic polyisocyanate is required for encapsulation, such as a high shear mixing apparatus, e.g. a blender, which will break the catalyst solution into a very fine dispersion.
- a capsule shell wall forms around each droplet of catalyst solution as a result of the reaction of the isocyanate at the droplets surface.
- the capsules obtained are a distribution of sizes generally ranging from about 1 to 20 microns in diameter. Because the capsules are small they can be evenly dispersed throughout the isocyanate material to provide a rapid, complete cure when activated.
- the preferred range of capsule diameters is about 1 microns, these diameters being easily dispersed; however, larger and smaller capsules also give useful isocyanatecatalyst compositions.
- the larger diameter capsules are produced by lower shear and vice versa.
- the formed capsules may be produced in concentrations of about 0.1 30 percent by weight of catalyst in the isocyanate. The system can be diluted with more polyisocyanate to reduce the catalyst concentration present.
- the amount of catalyst contained in the diluted isocyanate-catalyst systems is generally about 0.1 5 percent by weight of the isocyanate material to be trimerized. Functionally stated, the amount of catalyst present is preselected to be that amount which will catalyze a particular isocyanate material to a fully cured isocyanurate resin. Simple empirical tests are adequate to show the amount of encapsulated catalyst needed in any given system.
- aromatic polyisocyanate materials which can be trimerized to isocyanurates with the encapsulated catalysts of this invention are known.
- Particularly useful isocyanates can be represented by the formula R(NCO),, where R is aryl or alkyl substituted alkaryl and n is 2 to 5 or higher.
- Examples of such isocyanates are 2,4- and 2,6-tolylene diisocyanates; 1,5- naphthalene diisocyanate; 4,4- diisocyantodiphenylmethane and 3,3'-dimethyl-4,4'- diphenylene diisocyanate.
- polymeric polyisocyanates can also be used, such as those obtained by phosgenation of polyamines, prepared by condensing formaldehyde with aromatic amines.
- Particularly useful polymeric polyisocyanates are the polymethylene polyphenyl polyisocyanates such as those sold commercially under the trademarks Mondur MR and MRS, (available from Mobay Co.), 901 and 390 P and PAPI (available from Upjohn). Lists of commercially available polyisocyanates are found in Kirk and Othmer, Encyclopedia of Chemical Technology, Vol. 12, 2nd Ed., pp.
- Urethane prepolymers sometimes referred to as isocyanate-terminated prepolymers, can also be trimerized and are known (e.g. see US. Pat. Nos. 3,073,802 and 3,054,755), such prepolymers being prepared by reacting aromatic or so-called polymeric polyisocyanates with a polyol such as polyoxyalkylene polyol, typ ically polyoxypropylene glycol, using excess isocyanate. Mixtures of polyisocyanates or polyols can be used to prepare isocyanateterminated prepolymers. In addition to polyoxyalkylene polyols, polyesters and polyamides containing reactive hydroxyl groups can be used.
- Suitable polyols for use in isocyanate-terminated urethane prepolymers can have varying molecular weights, for example between and 3,000 or even as high as 5,000. Where a harder polyisocyanurate is desired, the polyol will generally have a hydroxyl equivalent weight of about 45 400 (i.e. 1 reactive hydroxyl group per 45 400 molecular weight of polyol). Where a softer, tougher polyisocyanurate is desired, the polyol will generally have a molecular weight of 400 to 1,000 or higher.
- the polyoxyalkylene polyols are generally condensates of ethylene, propylene or butylene oxides with glycerol, pentaerythritol, sorbitol, sucrose, methylglucosides or low molecular polyols, such as propylene glycol, tri-, tetra-, penta-, hexa-methylene glycols, l,3- butylene glycol, l,3(2-ethyl)hexanedoil, 2,2,4- trimethyl-l,3-pentanediol, trimethylol propane, 1,2,6- hexanetriol, or phenyldiisopropanolamine.
- the mixtures can have NCO/OH equivalent ratios greater than 1, preferably at least 1.2/1 to 6/1. Generally, the greater the amount of isocyanurate in the resulting product the greater its hardness.
- the preferred products are those which are highly crosslinked by reason of having about 20% to 85% of the isocyanate groups in the reaction mixture converted to isocyanurate linkages or when moisture is present during polymerization, also urea linkages.
- a polyol-diisocyanate starting mixture can include a conventional triisocyanate or triol.
- the mixture can also include modifying mono-isocyanates or alcohols such as 1,4-butane diol, butyl Cellosolve, butyl Car- 'bitol and oleyl alcohol to impart special properties to the polymer product, such as the degree of final hardness.
- Filled resin products can be made by incorporating into the preformed isocyanate-catalyst system a host of different powderd, granular, particulate, fibrous or finely divided fillers such as clay, talc, glass beads or bubbles, metal powders, rubbery granular aggregate such as scrap rubber obtained from tires, pigments, e.g., titanium dioxide, carbon black, etc., diatomaceous earth, glass fibers and the like.
- the fillers can be added in amounts of 5 to percent by weight of isocyanate material.
- trasonic, microwave and dielectric means Successful thermal activation requires that the encapsulated composition be heated above ambient temperature, such as above 50C. and preferably above about 75C., for a sufficient length of time to achieve release of the catalyst from the capsule and initiate trimerization. Once trimerization is initiated, the reaction is exothermic and will continue to completion even though the activating condition is removed.
- Solvents may be used to activate the catalystisocyanate system of this invention.
- a suitable amount of a polar solvent added to the system causes diffusion of the catalyst through the capsule shell wall.
- suitable activating solvents are dimethylformamide, N-methyl pyrrolidinone; dimethylsulfoxide, as well as polyols and alcohols.
- Monofunctional alcohols are generally not suitable activating agents since they react with isocyanate to chain terminate the prepolymer inhibiting trimerization, and primary and secondary aliphatic amines react with the isocyanate too rapidly to cause good diffusion of the isocyanate through the capsule shell wall.
- Exposure of the isocyanate-catalyst system to microwave ultrasonic energy or other energy forms can cause sufficient release of the catalyst from the capsules to initiate polymerization.
- Gel times of the isocyanate-catalyst system of this invention after activation are usually a few seconds with complete curing being achieved in a few minutes depending on the amount of catalyst released and the temperature of the cure.
- the behavior of the encapsulated isocyanate-catalyst system is at variance with the behavior of prior art isocyanurate-catalyst systems orthe prior art encapsulated systems.
- Prior art encapsulated systems require hours to initiate reaction when activated, in contrast to applicants system which requires only a few seconds to minutes before gelling after activation.
- the one-part encapsulated catalyst-polyisocyanate compositions of this invention are useful as adhesives, paints, coatings, and for use in reinforced laminates, e.g. plywood fabrication and patching, and composites.
- the laminates and composites can be prefabricated and the resin system activated in place by heating or other methods such as those disclosed hereinbefore.
- a variety of fillers may be incorporated into the resin systems of this invention so that significantly higher viscosity prepolymer materials are obtained.
- Thixotropic characteristics may also be obtained when thixotropic agents, e.g. Cabosil are included in the formulations.
- thixotropic agents e.g. Cabosil are included in the formulations.
- These resin compositions, whether filled or unfilled, are capable of forming useful bonds to a variety of surfaces.
- Metals e.g. aluminum, steel or copper and polymeric surfaces, e.g. polyesters, polyamides, polyimides, urethanes and rubbers can be adhered together using the resin systems. Good adhesive bonds may also be formed between metallic and polymeric surfaces.
- compositions which have been shown to be useful for repairing wood and plywood may be prepared in the following manner.
- a resin system of polyisocyanate containing about 2% by weight of the microencapsulated catalyst of the invention is compounded with a generally non-reactive granular or fibrous filler such as Cabosil, clay, barium, sulfate, mica, etc. Glass or plastic bubbles and pigments may also be added.
- the glass microbubbles or plastic microballoons are included to make a lighweight polyisocyanurate composition with improved staining characteristics.
- the other fillers present are useful for cost reduction, improved handling properties of the uncured resin, improved physical properties of the finally cured resin, and pigmentation.
- the exact amounts of the fillers that are employed may be varied from about 5 to 50 percent by volume of the cured composition depending upon the needed properties of the finally cured composition and the density of the filler.
- the resin-filler may be triggered by the same methods prevously described to give a useful patching composition.
- a conventional plywood sheet with imperfections in the wood is prepared for patching by routing or removing a small amount of wood in the patch area so that a uniform cavity is obtained. This cavity may be as deep and wide as necessary to remove weak and undesirable-appearing wood from the sheet.
- the sheet is then heated for several seconds with a radiant heater to about 100C. followed by addition of the patching composition while providing mechanical shear. Subsequent heating at 100 to 150C. is performed until the triggered release of catalyst has occurred and sufficient curing has been obtained to make it possible to sand the patched area smooth; typically, 1 to 2 minutes.
- the entire plywood composition may then be stained with good color matching characteristics depending upon the filler used in the resin system.
- the one-part isocyanate-catalyst systems of this invention may also be employed as one-part foamproducing compositions which are useful as void fillers and thermal insulators.
- Foams of low density can be prepared by incorporating blowing agents plus a surfactant into the preformed isocyanate-catalyst system.
- blowing agents are low boiling hydrocarbons, e.g. pentane, hexanes, heptane, octene; halogenated hydrocarbons such as dichlorodifluoromethane, dichlorodifluoroethane, trichlorofluoromethane, isopropylchloride, methylene chloride, etc.
- the density will vary depending on the blowing agent, surfactant and isocyanate-catalyst system used.
- EXAMPLE 1 A variable speed laboratory type Waring Blender having a capacity of approximately 1 liter was charged with 300 parts of Mondur MRS (polymethylene polyphenyl polyisocyanate, having an isocyanate functionality of about 2.7). The blender was turned on and its speed increased to maximum followed by the rapid addition of 40 parts of a solution containing percent by weight potassium lactate in glycerol, (having a viscosity of 320,000 centipoise) over a period of about one-fourth minute. A fine dispersion of liquid catalyst droplets was formed in the isocyanate. The blender was stopped and the dispersion degassed in a vacuum desiccator.
- Mondur MRS polymethylene polyphenyl polyisocyanate, having an isocyanate functionality of about 2.7
- the blender was turned on and its speed increased to maximum followed by the rapid addition of 40 parts of a solution containing percent by weight potassium lactate in glycerol, (having a viscosity of 320,000 centip
- an encapsulating shell formed around each droplet which occurred by reaction of the catalyst solution with isocyanate material.
- the isocyanate-catalyst system concentrate was diluted with 8 parts of an isocyanateterminated prepolymer made by: reacting 75 parts of Mondur MRS with 25 parts of polyoxypropyleneglycol 901, 300 parts of lsonate 39OP and 300 parts of PAP], for the Mondur MRS.
- the resulting isocyanate-catalyst system concentrates were diluted to about 1% catalyst concentration with isocyanate material in a manner similar to Example 1.
- the resulting systems cured in about 2 minutes to isocyanurate resins having 50 90 Shore D hardness when activated at temperatures between 90 and 100C. and cured in 5 minutes when solventactivated with dimethylformamide, dimethylsulfoxide or N-methyl pyrrolidone.
- EXAMPLE 4 isocyanate-catalyst systems concentrates were prepared in a continuous process by pumping Mondur MRS polyisocyanate and 75% potassium lactate solution in glycerol through a continuous mixing blender.
- the blender a variable speed OAKES blender, was fitted with two pumps which continuously fed isocyanate and catalyst into the blending head.
- the polyisocyanate flow rate was varied from 500 to 680 milliliters per minute, the lactate solution from 30 to 90 milliliters per minutes, and the shear setting from 4 to 9.
- the microcapsules obtained were similar in activity to those obtained in Example 1.
- the average size of the capsules ranged from 1 to 10 microns depending on the flow rates and the shear setting of the blender; the lower flow rates and higher shear settings giving smaller capsules sizes, and higher flow rates and lower shear settings giving larger capsules.
- EXAMPLE 5 One hundred and sixty parts of an isocyanate-catalyst system concentrate prepared as in Example 4 using an isocyanate flow rate of 600 milliliters per minute, a lac- (l) The 80% solution has a viscosity of about 300,000 ccntipoise at 25C. (2) The 157: solution has a viscosity of about 5000 centipoise at 25C. (3) 80 parts of the catalyst-solvent was used for 300 grams MRS.
- Example 3 The procedure of Example 1 was repeated, substituting 300 parts of lsonate 143L, 300 parts of Isonate having a molecular weight of 2000 (available from 5 Union Carbide Corporation as PPG 2025). A portion of the mixture was cured by placing in an oven at 90C. for 2 minutes. The resulting cured polyisocyanurate resin obtained had a Shore D hardness of 80 85.
- the isocyanatecapsule catalyst system concentrate was diluted with several volumes of toluene, filtered, washed. with hexane and dried to free-flowing microcapsules. On redispersion of these capsules to form a 2% concentration of catalyst in isocyanate material, the resulting system cured, at a reduced rate compared to systems contaiing non-dried capsules.
- Example 2 The process of Example 1 was repeated using 40 parts of the catalysts and solvents shown in Table l in place of 75% potassium lactate in glycerol; each of the solutions being added to 300 parts of Mondur MRS. All of the materials made an encapsulated catalyst suitable for catalyzing isocyanurate formation.
- Catalyst Solvent (by weight) Solvent sodium lactate 50 glycerol potassium lactate 80 (l) glycerol potassium lactate 75 glycerol potassium lactate (3) l5 (2) glycerol potassium lactate 50 ethylene glycol potassium lactate 50 propylene glycol potassium lactate 50 oxydiethanol rubidium lactate 50 glycerol potassium glycolate 50 glycerol potassium- 50 glycerol hydroxyisobutyrate potassium 50 glycerol p-Cl-phenoxide potassium mandelate 50 glycerol complex of monopotassium 67 ethylene glycol ethylene-glycolate with trimethyl borate potassium cyanoacetate 33 glycerol potassium 50 glycerol B-hydroxypropionate potassium 50 glycerol fi-hydroxybutyrate potassium acetate 40 glycerol potassium ethyl xanthate 40 glycerol potassium methoxy acetate glycerol
- a 10 gram sample of the isocyanate-catalyst system was placed in a small aluminum dish, heated at 150C. in an oven for 2 minutes, removed from the oven and cooled to room temperature.
- the resulting resin had a Shore D hardness of 85 88.
- a 10 gram sample of the isocyanate-catalyst system was cured by exposure to microwave energy having a wavelength of 2.45 GHz for 2 to 5 minutes using a Litton Microwave Oven.
- the resulting mixture cured in about 2 5 minutes to an isocyanurate-resin having a hardness of 60 to 65 Shore D.
- a gram sample of the isocyanate-catalyst system was cured by exposing the resin to ultrasonic energy (BioSonic II Ultrasonic Probe manufactured by Bronwill Scientific) producing 125 watts of ultrasonic energy at 200 kilocycles.
- the resulting mixture cured to an isocyanurate-urethane resin having a Shore D hardness of 80 to 90 in about 5 minutes.
- a patching composition was prepared as follows: 74 parts of a system of an isocyanate-terminated prepolymer (prepared from 60% Mondur MRS and 40% polyoxypropylene glycol having 2000 molecular weight) containing 2% encapsulated potassium lactate by weight 6 parts glass bubbles B--B (available from 3M Company) 16 parts clay 5 parts Burnt Umber 671 (available from Hercule Inc.) 2.5 parts red iron oxide 0.5 part carbon black The above ingredients were mixed until homogeneously dispersed and then degassed under vacuum prior to curing on the wood sample. The composition was used to fill imperfections in plywood and cured by exposure for a few seconds to radiant heat. The plywood patch could then be sanded and machined satisfactorily.
- EXAMPLE 7 A patching composition was prepared as follows: 64 parts of the isocyanate-terminated prepolymercatalyst mixture used in Example 6 32 parts clay 5 parts Burnt Umber 671 available from Hercules Inc. 2.5 parts red iron oxide 0.5 part carbon black The above ingredients were mixed until homogeneously dispersed and then degassed under vacuum to give a patching composition stable under storage conditions for a prolonged period of time (e.g., about 1 year). The composition was used to fill imperfections in plywood and cured by exposure to radiant heat for a few seconds. The dark colored patch could then be sanded, machined and painted satisfactorily.
- EXAMPLE 8 A patching composition was prepared as follows: 74 parts of the isocyanate-terminated prepolymercatalyst mixture used in Example 6 6 parts glass bubbles 20 parts clay 5 parts titanium dioxide After mixing and degassing the above ingredients, a composition was obtained which had prolonged stablity against polymerization under storage conditions. It was used to fill imperfections in wood and cured by radiant heat to provide repaired wood that was aesthetically appealing in appearance. The wood could be readily sanded, machined and painted on the repaired areas, providing uniform matching of properties between patched and unpatched areas.
- EXAMPLE 9 An isocyanate-catalyst system was prepared by adding 1 part of isocyanate-encapsulated catalyst system concentrate prepared as in Example 1 to nine parts of tolylene diisocyanate endcapped polytetramethyleneglycol having an NCO equivalent weight of 450, (available from duPont as Adiprene L-315). The isocyanate-catalyst system possessed a shelf life greater than one year at room temperature.
- the isocyanate-catalyst system was used as an adhesive to bond natural rubber to steel by coating steel samples with a thin, about 1 mil, layer of resin, pressing a strip of natural rubber on the samples, and heating the assemblies for 5 minutes in an oven at C. whereon the system cured to an isocyanurate resin.
- the following bond strengths were obtained:
- EXAMPLE 12 A one-part isocyanurate foaming composition was prepared as follows:
- EXAMPLE 13 250 parts of the isocyanate-catalyst-surfactant system of Example 2 were homogeneously mixed with 15 parts of Freon 113 (a fluorinated-chlorinated hydrocarbon available from E. l. duPont Company). Upon heating at 300F. for 5 minutes, a rigid isocyanurate foam having a density of approximately 6 pounds per cubic foot was obtained.
- Freon 113 a fluorinated-chlorinated hydrocarbon available from E. l. duPont Company
- a room-temperature latent, curable system comprising:
- an encapsulated liquid catalyst having a viscosity greater than about 5,000 centipoise at 25C., for the trimerization of said polyisocyanate dispersed throughout said system, said liquid catalyst being encapsulated in capsules having a permeable shell wall comprising partially polymerized isocyanate, said permeable capsule shell wall being impermeable to said liquid catalyst at room temperature but permeable to said catalyst at temperatures above about C.
- aromatic polyisocyanate is a polymethylene polyphenyl polyisocyanate.
- liquid catalyst is a metal salt of an organic acid in polyol solution.
- a method for forming a room temperature latent, isocyanate-catalyst system comprising the steps of:
- liquid isocyanurate trimerization catalyst having a viscosity of at least about 5,000 centipoise at 25C., and an aromatic polyisocyanate under conditions of high shear to form a dipersion of droplets, of catalyst in said polyisocyanate;
- a process for curing a room-temperature latent curable system comprising an aromatic polyisocyanate and an encapsulated liquid catalyst in a capsule having a permeable shell wall impermeable to said catalyst at room temperature, comprising the step of:
- compositionof claim 1 containing a chemical blowing agent and surfactant for polyisocyanurate foam formation.
- liquid catalyst is a metal salt solution of an organic acid in a polar solvent.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US402409A US3860565A (en) | 1973-10-01 | 1973-10-01 | Encapsulated isocyanurate catalyst |
ZA00745229A ZA745229B (en) | 1973-10-01 | 1974-08-14 | Encapsulated isocyanurate catalyst |
CA207,569A CA1045287A (en) | 1973-10-01 | 1974-08-22 | Encapsulated isocyanurate catalyst |
SE7411846A SE421320B (sv) | 1973-10-01 | 1974-09-20 | Herdbar komposition innehallande aromatisk isocyanatmonomer med deri dispergerade katalysatorinnehallande kapslar, vars veggar er bildade av samma, delvis polymeriserade aromatiska polyisocyanatmonomer |
NO743405A NO145099C (no) | 1973-10-01 | 1974-09-20 | Isocyanat/katalysatorsystem og fremgangsmaate til dets fremstilling. |
ES430271A ES430271A1 (es) | 1973-10-01 | 1974-09-21 | Un metodo de formar un sistema de isocianato-catalizador latente a temperatura ambiente. |
DE2447143A DE2447143C2 (de) | 1973-10-01 | 1974-09-30 | Verfahren zur Herstellung eines lagerstabilen Polyisocyanat-Trimerisierungskatalysator-Systems |
JP49112704A JPS5818367B2 (ja) | 1973-10-01 | 1974-09-30 | ホウフウイソシアヌレ−トシヨクバイ |
AU73803/74A AU487148B2 (en) | 1973-10-01 | 1974-09-30 | Microencapsulated isocyanurate catalyst |
GB42290/74A GB1482545A (en) | 1973-10-01 | 1974-09-30 | Systems comprising an aromatic polyisocyanate and an encapsulated catalyst |
FI2849/74A FI58503C (fi) | 1973-10-01 | 1974-09-30 | Haerdbart aromatiskt isocyanat-katalysator-system |
BR8094/74A BR7408094D0 (pt) | 1973-10-01 | 1974-09-30 | Processo para formar um conjunto de catalisador-isocianato latente em temperatura ambiente |
IT53287/74A IT1019446B (it) | 1973-10-01 | 1974-09-30 | Perfezionamento nei procedimenti di fabbricazione di sistemi catalizzan ti isocianato |
FR7432815A FR2246308B1 (xx) | 1973-10-01 | 1974-09-30 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US402409A US3860565A (en) | 1973-10-01 | 1973-10-01 | Encapsulated isocyanurate catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
US3860565A true US3860565A (en) | 1975-01-14 |
Family
ID=23591766
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US402409A Expired - Lifetime US3860565A (en) | 1973-10-01 | 1973-10-01 | Encapsulated isocyanurate catalyst |
Country Status (13)
Country | Link |
---|---|
US (1) | US3860565A (xx) |
JP (1) | JPS5818367B2 (xx) |
BR (1) | BR7408094D0 (xx) |
CA (1) | CA1045287A (xx) |
DE (1) | DE2447143C2 (xx) |
ES (1) | ES430271A1 (xx) |
FI (1) | FI58503C (xx) |
FR (1) | FR2246308B1 (xx) |
GB (1) | GB1482545A (xx) |
IT (1) | IT1019446B (xx) |
NO (1) | NO145099C (xx) |
SE (1) | SE421320B (xx) |
ZA (1) | ZA745229B (xx) |
Cited By (52)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3963680A (en) * | 1975-03-17 | 1976-06-15 | Minnesota Mining And Manufacturing Company | One-part, room-temperature latent, curable isocyanate compositions |
US4070346A (en) * | 1975-01-21 | 1978-01-24 | Bayer Aktiengesellschaft | Production of polyurethane powder |
US4098730A (en) * | 1975-09-23 | 1978-07-04 | Metallgesellschaft Aktiengesellschaft | Non-flammable organo-red mud polymers, some of which are electrically conductive, and process for their manufacture |
US4100148A (en) * | 1975-06-13 | 1978-07-11 | Rutgerswerke Aktiengesellschaft | Storage-stable, very quickly hardenable, one-component sealant based on mercapto-terminated polymers |
US4225460A (en) * | 1979-06-28 | 1980-09-30 | Minnesota Mining And Manufacturing Company | Latent Lewis acid catalyst system and process |
US4230809A (en) * | 1977-12-21 | 1980-10-28 | Hoechst Aktiengesellschaft | Pressure-resistant polyurethane-polyurea particles for the encapsulation of active ingredients and process for their manufacture |
US4237252A (en) * | 1979-06-28 | 1980-12-02 | Minnesota Mining And Manufacturing Company | Heat activatable one-part liquid resin systems |
US4252708A (en) * | 1979-06-28 | 1981-02-24 | Minnesota Mining And Manufacturing Company | Mechanically activateable one-part liquid resin systems |
US4260728A (en) * | 1980-05-05 | 1981-04-07 | Olin Corporation | Preparation of noncellular polyurethane compositions |
US4288587A (en) * | 1980-05-05 | 1981-09-08 | Olin Corporation | Preparation of noncellular polyurethane compositions |
EP0039137A1 (en) * | 1980-04-30 | 1981-11-04 | Imperial Chemical Industries Plc | Isocyanate reactions |
WO1984001919A1 (en) * | 1982-11-12 | 1984-05-24 | Dougherty Michael J | Process for the manufacture of products from reinforced polyester resins |
US4524043A (en) * | 1982-11-12 | 1985-06-18 | Mcdougal John R | Process for the manufacture of products from reinforced polyester resins |
US4546165A (en) * | 1984-02-02 | 1985-10-08 | Bayer Aktiengesellschaft | Process for the production of stabilized polyisocyanates of retarded reactivity and their use in the production of polyurethanes |
US4565764A (en) * | 1982-09-10 | 1986-01-21 | Canon Kabushiki Kaisha | Microcapsule toner and process of making same |
US4624814A (en) * | 1982-11-12 | 1986-11-25 | Mcdougal John R | Process for the manufacture of products from reinforced polyester resins |
US4647418A (en) * | 1982-11-12 | 1987-03-03 | Mcdougal John R | Process for the manufacture of products from reinforced polyester |
EP0224382A2 (en) * | 1985-11-21 | 1987-06-03 | LOCTITE (IRELAND) Ltd. | Method of activating chemical compositions |
EP0257467A2 (en) * | 1986-08-22 | 1988-03-02 | General Electric Company | Composition and method for controlling polymerization rate of cyclic polycarbonate oligomers |
US4798856A (en) * | 1987-11-06 | 1989-01-17 | Columbian Chemicals Co. | Pigment dispersion in resin |
US4829097A (en) * | 1986-01-22 | 1989-05-09 | Oy Lohja Ab | Process for the preparation of an isocyanurate modified polyurethane foam and the resulting foam |
EP0380178A2 (en) * | 1989-01-27 | 1990-08-01 | HENKEL S.p.A. | Use of crosslinkable hot melt adhesive compositions |
US4991362A (en) * | 1988-09-13 | 1991-02-12 | Minnesota Mining And Manufacturing Company | Hand scouring pad |
US5084494A (en) * | 1982-11-12 | 1992-01-28 | Mcdougal John R | Polyester resin and reinforcement composite materials |
US5102969A (en) * | 1988-07-21 | 1992-04-07 | Teroson G.M.B.H. | Process for the production of a sealing and adhesive compound strip and device for implementing this process |
US5134774A (en) * | 1991-03-11 | 1992-08-04 | Arc Plan, Inc. | Anchoring method for hydraulic turbine repair |
US5401505A (en) * | 1991-03-28 | 1995-03-28 | Minnesota Mining And Manufacturing | Microcapsules from polyfunctional aziridines |
US5433953A (en) * | 1994-01-10 | 1995-07-18 | Minnesota Mining And Manufacturing | Microcapsules and methods for making same |
US5634743A (en) * | 1995-06-10 | 1997-06-03 | Sound Pipe, Ltd. | Lining of pipelines and passageways |
US5726456A (en) * | 1995-02-17 | 1998-03-10 | Gel Sciences, Inc. | Encapsulated materials |
US5849412A (en) * | 1995-02-17 | 1998-12-15 | Medlogic Global Corporation | Encapsulated materials |
US5905151A (en) * | 1993-02-18 | 1999-05-18 | Bayer Corporation | Trimer catalyst for aliphatic and aromatic isocyanates |
US5958863A (en) * | 1995-04-27 | 1999-09-28 | Witco Corporation | Cationic compositions containing diol alkoxylate |
US20060047010A1 (en) * | 2004-09-02 | 2006-03-02 | O'leary Robert J | Pseudo one part foam |
US20070135608A1 (en) * | 2005-12-09 | 2007-06-14 | Bayer Materialscience Ag | Process for the preparation of polyisocyanates containing carbodiimide and/or uretonimine groups |
US20070197670A1 (en) * | 2006-02-23 | 2007-08-23 | International Business Machines Corporation | Rigidized compliant foam and method for implementing a rigidized compliant foam |
EP0935630B2 (en) † | 1996-11-01 | 2009-03-11 | Bayer Corporation | Amine-initiated polyether polyols and a process for their production |
US20090078918A1 (en) * | 2007-09-25 | 2009-03-26 | Cary Michael Huettner | Methods and Structures With Fire Retardant Spheres for Implementing Enhanced Fire Protection |
US20100326813A1 (en) * | 2005-03-11 | 2010-12-30 | New Jersey Institute Of Technology | Microwave Induced Functionalization of Single Wall Carbon Nanotubes and Composites Prepared Therefrom |
US8642057B2 (en) | 2008-01-18 | 2014-02-04 | Biolargo Life Technologies, Inc. | Antimicrobial and antiodor solutions and delivery systems |
US8846067B2 (en) | 2008-01-18 | 2014-09-30 | Kenneth R. Code | Antimicrobial solutions and methods |
US20150132497A1 (en) * | 2013-11-08 | 2015-05-14 | Ppg Industries Ohio, Inc. | Curable film-forming composition comprising catalyst associated with a carrier |
US20160090455A1 (en) * | 2014-09-23 | 2016-03-31 | The Boeing Company | Polymer nanoparticles for controlling resin reaction rates |
AU2014346949B2 (en) * | 2013-11-08 | 2017-01-19 | Ppg Industries Ohio, Inc. | Curable film-forming compositions comprising catalyst associated with a carrier and methods for coating a substrate |
US9862828B2 (en) | 2014-09-23 | 2018-01-09 | The Boeing Company | Polymer nanoparticle additions for resin modification |
US10072126B2 (en) | 2014-09-23 | 2018-09-11 | The Boeing Company | Soluble nanoparticles for composite performance enhancement |
US10160840B2 (en) | 2014-09-23 | 2018-12-25 | The Boeing Company | Polymer nanoparticles for controlling permeability and fiber volume fraction in composites |
US10238990B2 (en) | 2008-01-18 | 2019-03-26 | Kenneth R. Code | Apparatus for removing contamination via electrodes and a two-layered filter comprising carbon and an activating agent |
US10662302B2 (en) | 2014-09-23 | 2020-05-26 | The Boeing Company | Polymer nanoparticles for improved distortion capability in composites |
WO2020126778A1 (en) | 2018-12-19 | 2020-06-25 | Covestro Intellectual Property Gmbh & Co. Kg | Thermolatent catalyst for polymerization of isocyanates |
WO2021069335A1 (en) | 2019-10-07 | 2021-04-15 | Covestro Intellectual Property Gmbh & Co. Kg | Storage-stable thermolatent catalysts for the polymerization of isocyanates |
EP4025662A4 (en) * | 2019-09-06 | 2023-09-27 | The Willamette Valley Company, Llc | TWO-COMPONENT URETHANE FOR REPAIR OF WOOD AND WOOD PRODUCTS AND METHODS OF USE THEREOF |
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US9018327B1 (en) | 2013-11-08 | 2015-04-28 | Ppg Industries Ohio, Inc. | Catalyst compositions and methods of preparing them |
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US3455848A (en) * | 1964-05-05 | 1969-07-15 | Ncr Co | Polyurethane foam-producing compositions comprising microencapsulated particles and a method of making foams therefrom |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL300468A (xx) * | 1962-11-24 | |||
DE2312059A1 (de) * | 1972-03-15 | 1973-09-20 | Stauffer Chemical Co | Verfahren zum einkapseln mit wasser nicht mischbarer stoffe |
-
1973
- 1973-10-01 US US402409A patent/US3860565A/en not_active Expired - Lifetime
-
1974
- 1974-08-14 ZA ZA00745229A patent/ZA745229B/xx unknown
- 1974-08-22 CA CA207,569A patent/CA1045287A/en not_active Expired
- 1974-09-20 NO NO743405A patent/NO145099C/no unknown
- 1974-09-20 SE SE7411846A patent/SE421320B/xx not_active IP Right Cessation
- 1974-09-21 ES ES430271A patent/ES430271A1/es not_active Expired
- 1974-09-30 FI FI2849/74A patent/FI58503C/fi active
- 1974-09-30 BR BR8094/74A patent/BR7408094D0/pt unknown
- 1974-09-30 IT IT53287/74A patent/IT1019446B/it active
- 1974-09-30 DE DE2447143A patent/DE2447143C2/de not_active Expired
- 1974-09-30 JP JP49112704A patent/JPS5818367B2/ja not_active Expired
- 1974-09-30 FR FR7432815A patent/FR2246308B1/fr not_active Expired
- 1974-09-30 GB GB42290/74A patent/GB1482545A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3455848A (en) * | 1964-05-05 | 1969-07-15 | Ncr Co | Polyurethane foam-producing compositions comprising microencapsulated particles and a method of making foams therefrom |
Cited By (67)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4070346A (en) * | 1975-01-21 | 1978-01-24 | Bayer Aktiengesellschaft | Production of polyurethane powder |
US3963680A (en) * | 1975-03-17 | 1976-06-15 | Minnesota Mining And Manufacturing Company | One-part, room-temperature latent, curable isocyanate compositions |
US4100148A (en) * | 1975-06-13 | 1978-07-11 | Rutgerswerke Aktiengesellschaft | Storage-stable, very quickly hardenable, one-component sealant based on mercapto-terminated polymers |
US4098730A (en) * | 1975-09-23 | 1978-07-04 | Metallgesellschaft Aktiengesellschaft | Non-flammable organo-red mud polymers, some of which are electrically conductive, and process for their manufacture |
US4230809A (en) * | 1977-12-21 | 1980-10-28 | Hoechst Aktiengesellschaft | Pressure-resistant polyurethane-polyurea particles for the encapsulation of active ingredients and process for their manufacture |
US4225460A (en) * | 1979-06-28 | 1980-09-30 | Minnesota Mining And Manufacturing Company | Latent Lewis acid catalyst system and process |
US4237252A (en) * | 1979-06-28 | 1980-12-02 | Minnesota Mining And Manufacturing Company | Heat activatable one-part liquid resin systems |
DE3024264A1 (de) * | 1979-06-28 | 1981-01-08 | Minnesota Mining & Mfg | Latentes katalysatorkonzentrat |
FR2460157A1 (fr) * | 1979-06-28 | 1981-01-23 | Minnesota Mining & Mfg | Catalyseur latent a base d'acides de lewis et son procede de production |
US4252708A (en) * | 1979-06-28 | 1981-02-24 | Minnesota Mining And Manufacturing Company | Mechanically activateable one-part liquid resin systems |
EP0039137A1 (en) * | 1980-04-30 | 1981-11-04 | Imperial Chemical Industries Plc | Isocyanate reactions |
US4260728A (en) * | 1980-05-05 | 1981-04-07 | Olin Corporation | Preparation of noncellular polyurethane compositions |
US4288587A (en) * | 1980-05-05 | 1981-09-08 | Olin Corporation | Preparation of noncellular polyurethane compositions |
US4565764A (en) * | 1982-09-10 | 1986-01-21 | Canon Kabushiki Kaisha | Microcapsule toner and process of making same |
WO1984001919A1 (en) * | 1982-11-12 | 1984-05-24 | Dougherty Michael J | Process for the manufacture of products from reinforced polyester resins |
GB2146283A (en) * | 1982-11-12 | 1985-04-17 | John R Mcdougal | Process for the manufacture of products from reinforced polyester resins |
US4524043A (en) * | 1982-11-12 | 1985-06-18 | Mcdougal John R | Process for the manufacture of products from reinforced polyester resins |
US5084494A (en) * | 1982-11-12 | 1992-01-28 | Mcdougal John R | Polyester resin and reinforcement composite materials |
US4624814A (en) * | 1982-11-12 | 1986-11-25 | Mcdougal John R | Process for the manufacture of products from reinforced polyester resins |
US4647418A (en) * | 1982-11-12 | 1987-03-03 | Mcdougal John R | Process for the manufacture of products from reinforced polyester |
US4546165A (en) * | 1984-02-02 | 1985-10-08 | Bayer Aktiengesellschaft | Process for the production of stabilized polyisocyanates of retarded reactivity and their use in the production of polyurethanes |
US4867817A (en) * | 1985-11-21 | 1989-09-19 | Loctite (Ireland) Limited | Method and device for activating chemical compositions |
EP0224382B1 (en) * | 1985-11-21 | 1991-03-06 | LOCTITE (IRELAND) Ltd. | Method of activating chemical compositions |
EP0224382A2 (en) * | 1985-11-21 | 1987-06-03 | LOCTITE (IRELAND) Ltd. | Method of activating chemical compositions |
US4829097A (en) * | 1986-01-22 | 1989-05-09 | Oy Lohja Ab | Process for the preparation of an isocyanurate modified polyurethane foam and the resulting foam |
EP0257467A2 (en) * | 1986-08-22 | 1988-03-02 | General Electric Company | Composition and method for controlling polymerization rate of cyclic polycarbonate oligomers |
EP0257467A3 (en) * | 1986-08-22 | 1989-07-19 | General Electric Company | Composition and method for controlling polymerization rate of cyclic polycarbonate oligomers |
US4798856A (en) * | 1987-11-06 | 1989-01-17 | Columbian Chemicals Co. | Pigment dispersion in resin |
US5102969A (en) * | 1988-07-21 | 1992-04-07 | Teroson G.M.B.H. | Process for the production of a sealing and adhesive compound strip and device for implementing this process |
US4991362A (en) * | 1988-09-13 | 1991-02-12 | Minnesota Mining And Manufacturing Company | Hand scouring pad |
EP0380178A2 (en) * | 1989-01-27 | 1990-08-01 | HENKEL S.p.A. | Use of crosslinkable hot melt adhesive compositions |
EP0380178A3 (en) * | 1989-01-27 | 1991-02-06 | HENKEL S.p.A. | Use of crosslinkable hot melt adhesive compositions |
US5134774A (en) * | 1991-03-11 | 1992-08-04 | Arc Plan, Inc. | Anchoring method for hydraulic turbine repair |
US5401505A (en) * | 1991-03-28 | 1995-03-28 | Minnesota Mining And Manufacturing | Microcapsules from polyfunctional aziridines |
US5905151A (en) * | 1993-02-18 | 1999-05-18 | Bayer Corporation | Trimer catalyst for aliphatic and aromatic isocyanates |
US5433953A (en) * | 1994-01-10 | 1995-07-18 | Minnesota Mining And Manufacturing | Microcapsules and methods for making same |
US6013698A (en) * | 1995-02-17 | 2000-01-11 | Medlogic Global Corporation | Encapsulated materials |
US5726456A (en) * | 1995-02-17 | 1998-03-10 | Gel Sciences, Inc. | Encapsulated materials |
US5789494A (en) * | 1995-02-17 | 1998-08-04 | Medlogic Global Corporation | Encapsulated materials |
US5849412A (en) * | 1995-02-17 | 1998-12-15 | Medlogic Global Corporation | Encapsulated materials |
US5932285A (en) * | 1995-02-17 | 1999-08-03 | Medlogic Global Corporation | Encapsulated materials |
US5958863A (en) * | 1995-04-27 | 1999-09-28 | Witco Corporation | Cationic compositions containing diol alkoxylate |
US5634743A (en) * | 1995-06-10 | 1997-06-03 | Sound Pipe, Ltd. | Lining of pipelines and passageways |
EP0935630B2 (en) † | 1996-11-01 | 2009-03-11 | Bayer Corporation | Amine-initiated polyether polyols and a process for their production |
US20060047010A1 (en) * | 2004-09-02 | 2006-03-02 | O'leary Robert J | Pseudo one part foam |
US9249528B2 (en) * | 2005-03-11 | 2016-02-02 | New Jersey Institute Of Technology | Microwave induced functionalization of single wall carbon nanotubes and composites prepared therefrom |
US20100326813A1 (en) * | 2005-03-11 | 2010-12-30 | New Jersey Institute Of Technology | Microwave Induced Functionalization of Single Wall Carbon Nanotubes and Composites Prepared Therefrom |
US20070135608A1 (en) * | 2005-12-09 | 2007-06-14 | Bayer Materialscience Ag | Process for the preparation of polyisocyanates containing carbodiimide and/or uretonimine groups |
US20070197670A1 (en) * | 2006-02-23 | 2007-08-23 | International Business Machines Corporation | Rigidized compliant foam and method for implementing a rigidized compliant foam |
US20090078918A1 (en) * | 2007-09-25 | 2009-03-26 | Cary Michael Huettner | Methods and Structures With Fire Retardant Spheres for Implementing Enhanced Fire Protection |
US8642057B2 (en) | 2008-01-18 | 2014-02-04 | Biolargo Life Technologies, Inc. | Antimicrobial and antiodor solutions and delivery systems |
US8846067B2 (en) | 2008-01-18 | 2014-09-30 | Kenneth R. Code | Antimicrobial solutions and methods |
US10238990B2 (en) | 2008-01-18 | 2019-03-26 | Kenneth R. Code | Apparatus for removing contamination via electrodes and a two-layered filter comprising carbon and an activating agent |
US10221315B2 (en) * | 2013-11-08 | 2019-03-05 | Ppg Industries Ohio, Inc. | Curable film-forming composition comprising catalyst associated with a carrier |
US11981832B2 (en) | 2013-11-08 | 2024-05-14 | Ppg Industries Ohio, Inc. | Curable film-forming compositions comprising catalyst associated with a carrier and methods for coating a substrate |
AU2014346949B2 (en) * | 2013-11-08 | 2017-01-19 | Ppg Industries Ohio, Inc. | Curable film-forming compositions comprising catalyst associated with a carrier and methods for coating a substrate |
US20150132497A1 (en) * | 2013-11-08 | 2015-05-14 | Ppg Industries Ohio, Inc. | Curable film-forming composition comprising catalyst associated with a carrier |
US9587076B2 (en) * | 2014-09-23 | 2017-03-07 | The Boeing Company | Polymer nanoparticles for controlling resin reaction rates |
US10160840B2 (en) | 2014-09-23 | 2018-12-25 | The Boeing Company | Polymer nanoparticles for controlling permeability and fiber volume fraction in composites |
US10072126B2 (en) | 2014-09-23 | 2018-09-11 | The Boeing Company | Soluble nanoparticles for composite performance enhancement |
US9862828B2 (en) | 2014-09-23 | 2018-01-09 | The Boeing Company | Polymer nanoparticle additions for resin modification |
US10662302B2 (en) | 2014-09-23 | 2020-05-26 | The Boeing Company | Polymer nanoparticles for improved distortion capability in composites |
US10995187B2 (en) | 2014-09-23 | 2021-05-04 | The Boeing Company | Composite structure having nanoparticles for performance enhancement |
US20160090455A1 (en) * | 2014-09-23 | 2016-03-31 | The Boeing Company | Polymer nanoparticles for controlling resin reaction rates |
WO2020126778A1 (en) | 2018-12-19 | 2020-06-25 | Covestro Intellectual Property Gmbh & Co. Kg | Thermolatent catalyst for polymerization of isocyanates |
EP4025662A4 (en) * | 2019-09-06 | 2023-09-27 | The Willamette Valley Company, Llc | TWO-COMPONENT URETHANE FOR REPAIR OF WOOD AND WOOD PRODUCTS AND METHODS OF USE THEREOF |
WO2021069335A1 (en) | 2019-10-07 | 2021-04-15 | Covestro Intellectual Property Gmbh & Co. Kg | Storage-stable thermolatent catalysts for the polymerization of isocyanates |
Also Published As
Publication number | Publication date |
---|---|
NO145099C (no) | 1982-01-13 |
DE2447143C2 (de) | 1983-12-29 |
NO145099B (no) | 1981-10-05 |
BR7408094D0 (pt) | 1975-07-22 |
GB1482545A (en) | 1977-08-10 |
FI58503B (fi) | 1980-10-31 |
FR2246308A1 (xx) | 1975-05-02 |
SE7411846L (xx) | 1975-04-02 |
JPS5062191A (xx) | 1975-05-28 |
JPS5818367B2 (ja) | 1983-04-12 |
ES430271A1 (es) | 1976-12-16 |
ZA745229B (en) | 1975-09-24 |
CA1045287A (en) | 1978-12-26 |
NO743405L (xx) | 1975-04-28 |
FI284974A (xx) | 1975-04-02 |
AU7380374A (en) | 1976-04-01 |
FR2246308B1 (xx) | 1978-06-09 |
DE2447143A1 (de) | 1975-04-03 |
IT1019446B (it) | 1977-11-10 |
SE421320B (sv) | 1981-12-14 |
FI58503C (fi) | 1981-02-10 |
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